Random-phase approximation vs Møller-Plesset perturbation theory for many-body energy contributions of hydrogen-bonded molecular solids

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F25%3A10508343" target="_blank" >RIV/00216208:11320/25:10508343 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=g6jf6.eiAa" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=g6jf6.eiAa</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1063/5.0292113" target="_blank" >10.1063/5.0292113</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Random-phase approximation vs Møller-Plesset perturbation theory for many-body energy contributions of hydrogen-bonded molecular solids

Popis výsledku v původním jazyce

The fragment-based approach is a promising strategy for applying correlated-wavefunction methods to lattice energies of molecular solids. A key requirement is the efficient inclusion of the long-distance and nonadditive contributions to the many-body expansion (MBE) of the lattice energy. This is especially important in crystals of polar molecules, where MBE converges slowly with distance. In this context, we compare the simplest coupled-cluster approach-the random-phase approximation (RPA)-against the well-established methodology of M &amp; oslash;ller-Plesset (MP) perturbation theory. Using the examples of solid ammonia, methanol, and formic acid, we show that the RPA with singles corrections based on the Kohn-Sham (KS) Perdew-Burke-Ernzerhof (PBE) orbitals yields near-benchmark accuracy for the two-body contributions. However, for any PBE-based variant of RPA, the three- and four-body contributions suffer from artifacts. For the nonadditive terms, the Hartree-Fock (HF) orbitals appear necessary. In fact, we find that the HF-based RPA with additional corrections recovers the nonadditive interactions about as accurately as the more expensive MP2.5 method. This is a departure from the typical KS-based RPA and an indication that the HF-based RPA can serve as an alternative to the usual MP methods in accurate approximations of the crystal lattice energy.

Název v anglickém jazyce

Random-phase approximation vs Møller-Plesset perturbation theory for many-body energy contributions of hydrogen-bonded molecular solids

Popis výsledku anglicky

The fragment-based approach is a promising strategy for applying correlated-wavefunction methods to lattice energies of molecular solids. A key requirement is the efficient inclusion of the long-distance and nonadditive contributions to the many-body expansion (MBE) of the lattice energy. This is especially important in crystals of polar molecules, where MBE converges slowly with distance. In this context, we compare the simplest coupled-cluster approach-the random-phase approximation (RPA)-against the well-established methodology of M &amp; oslash;ller-Plesset (MP) perturbation theory. Using the examples of solid ammonia, methanol, and formic acid, we show that the RPA with singles corrections based on the Kohn-Sham (KS) Perdew-Burke-Ernzerhof (PBE) orbitals yields near-benchmark accuracy for the two-body contributions. However, for any PBE-based variant of RPA, the three- and four-body contributions suffer from artifacts. For the nonadditive terms, the Hartree-Fock (HF) orbitals appear necessary. In fact, we find that the HF-based RPA with additional corrections recovers the nonadditive interactions about as accurately as the more expensive MP2.5 method. This is a departure from the typical KS-based RPA and an indication that the HF-based RPA can serve as an alternative to the usual MP methods in accurate approximations of the crystal lattice energy.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10302 - Condensed matter physics (including formerly solid state physics, supercond.)

Projekt

<a href="/cs/project/EH22_008%2F0004558" target="_blank" >EH22_008/0004558: Pokročilé víceškálové materiály pro nosné klíčové technologie</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Chemical Physics

ISSN

0021-9606

e-ISSN

1089-7690

Svazek periodika

163

Číslo periodika v rámci svazku

22

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

14

Strana od-do

224105

Kód UT WoS článku

001634622500001

EID výsledku v databázi Scopus

2-s2.0-105024066483